Tooth filling and facing compositions comprising a radiopaque glass and method of making the same

ABSTRACT

A filler composition for tooth filling and facing compositions comprising (1) a finely divided inorganic material, and (2) a barium aluminosilicate glass or other glass having an effective amount of radiopaque oxide that renders the resultant glass radiopaque to X-rays used by dentists. The filler composition is mixed with an organic polymer such as methyl methacrylate to provide a tooth filling and facing composition having an outstanding combination of desirable properties including a color resembling that of natural teeth, a suitable index of refraction, hardness, wear resistance, a relatively low thermal expansion matching that of natural teeth, and being radiopaque to X-rays used by dentists.

COMPOSITIONS COMPRISING A RADIOPAQUE GLASS AND METHOD OF MAKING THE SAME Related U.S. Application Data Division of Ser. No. 12,109, Feb. [7, 1970.

Inventor:

v United States Patent 1191' 1111 3,801,344 Dietz Apr. 2, 1974 [54] TOOTH FILLING AND FACING 3,541,688 11/1970 McLean et al 32/8 3,305,371 2/1967 de Lajarte 106/52 OTHER PUBLICATIONS Thomas, Journal of the American Ceramic Society, Vol. 33, pages 35-44 (Feb. 1950).

Primary Examiner-Allan Lieberman Attorney, Agent, or FirmRichard D. Heberling; E. J. Holler; John C. Smith, Jr.

[57] ABSTRACT A filler composition for tooth filling and facing compositions comprising (l) a finely divided inorganic material, and (2) a barium aluminosilicate glass or [52] U.S. Cl 106/300, 106/35, l06/39.6,

106/52, 106/288 B, 106/299, 106/303 other glass havlng an effective amount of rad1opaque 106/306, 260/41 A, 32/8, 32/12, 32/15 oxide that renders the resultant glass radiopaque to [51 m CL 1 00 CO9c 3 cog 3 X-rays used by dentists. The filler composition is 58 Field of Search 106/35, 39 DV, 52, 300, mixed with an Organic Polymer Such as methyl metha- 106/3O3 306 32/8 12 crylate to provide a tooth filling and facing composition having an outstanding combination of desirable 56] References Cited properties including a color resembling that of natural UNITED STATES PATENTS teeth, a sultable ndex of refract1on,-hard ness, wear reslstance, a relatlvely low thermal expansion match- S Py i 5% ing that of natural teeth, and being radiopaque to X- iege 3,467,534 9/1969 MacDowell 106/52 x rays used by 3,578,470 5/l973 Bahat et a] 106/39 DV 11 Claims, 1 Drawing Figure a 0 .fzo 6141151 ,d/A/ffll? aJ /kpr/oa/ COfFfid/EA/f: V; C'OMPdJ/f/DA (kjflqfifr'fl CfA/l') 29 4'70 7/ 70 I 60 Z f0\ The present application is a divisional of application set-saga? filed b-42.12791 THE INVENTION The present invention relates to a tooth filling and facing material having a combination of desirable properties including color resembling thatof natural teeth, a compatible index of refraction, strength, hardness, a thermal coefficient of expansion matching that of natural teeth, and being radiopaque to X-rays used by dentists. The invention particularly relates to a tooth filling and facing composition having a mixture of finely divided inorganic material and a radiopaque glass as a filler and an organic polymer as a binder.

In the past, there has been a problem in providing a suitable tooth filling and facing composition containing a filler composition and an organic polymer such as polymethyl methacrylate. The tooth filling and facing composition must have a combination of properties that includes a low coefficient of thermal expansion to 1 match that of natural teeth, strength, hardness, wear resistance, a color resembling that of natural teeth, and a compatible index of refraction while providing enough X-ray absorption to allow detection of the filled tooth. It has been difficult to provide a composition having all of the above-described properties, particularly one that has a thermal coefficient of expansion to match that of natural teeth and still is radiopaque to X- rays used by dentists.

lt is'an object of the present invention to provide a composition for use as a filler in tooth filling and facing compositions in which the filler composition comprises (1) a finely divided inorganic material and (2) a glass having an effective amount of a radiopaque producing oxide that renders the resultant galss radiopaque to X- rays used by dentists, the filler composition being capable of producing an outstanding tooth facing and filling material when mixed with an organic polymer, the resultant tooth repairing material having a combination of properties including a color resembling that of natural teeth, a suitable index of refraction, hardness, strength, wear resistance, a relatively low thermal expansion matching that of natural teeth, and being radiopaque to X-rays.

It is an object of the present invention to provide a filler composition for a tooth filling and facing composition and a method of making the filler composition and the tooth filling and facing composition.

These and other objects will be apparent from the specification that follows, theappended claims and the drawings in which:

The FIGURE is a ternary compositional diagram of sao-Ai,o,-sio, glass systems showing suitable and preferred glasses that are radiopaque to X-rays used by dentists and are adapted for use as fillers in tooth filling and facing compositions.

The present invention provides a filler composition for use as a filler and tooth facing and filling composition comprising a finely divided inorganic material and a glass having an effective amount of a radiopaque producing oxide that renders the resultant glass radiopaque to X-rays used by dentists. The resultant filler composition is incorporated in an organic binder such as an acrylic resin that produces a filling and facing composition that has a color resembling that of natural teeth, has a suitable index of refraction, has desired hardness and wear resistance, has relatively low thermal expansion matching that of natural teeth, and is radiopaque to X-rays used by dentists.

It is preferred that the radiopaque glass filler be a barium aluminosilicate glass with a 8210 content greater than about 22.5 percent by weight, such glass rendering the tooth filling and facing composition radiopaque to X-rays used by dentists. Furthermore, the resultant tooth filling and facing composition containing the barium aluminosilicate glass has a desirable color like that of natural teeth, a suitable index of refraction, high strength, wear resistance, a low thermal expansion matching that of natural teeth, and is nontoxic. Generally, the barium aluminosilicate glass is one consisting of BaO, A1 0 and SiO in the relative proportions by weight shown within the area marked by line I of the ternary diagram shown in the FIGURE. It is highly preferred that the radiopaque glass be one consisting essentially of BaO, A1 0 and SiO, in the relative proportions by weight shown inside the area marked by line II in the ternary diagram shown in the FIGURE. The optimum radiopaque glass is one consisting essentially of about 25-35 parts by weight of SiO 10-20 parts by weight of Al 0 and 50-60 parts by weight of BaO.

As previously indicated, a part of the filler composition is a finely divided inorganic material such as glassceramic material, quartz, fused silica, calcite, calcium carbonate, wollastonite, or other hard, finely divided inorganic filler having generally a mesh size of about 20 to 400 mesh, and preferably about to 200 mesh.

The filler composition which is inorganic material and the radiopaque glass is used in amounts of about 20-80 parts by weight with about 20-80 parts by weight of an organic polymer-binder. The organic polymer is preferably an acrylic resin such as polyethyl methacrylate, polyethyl acrylate and polymethyl methacrylate and it is highly preferred that the resin be polymethyl methacrylate.

The acrylic polymer can be prepared from a monomer or mixtures of monomers having the general formula CHi=c-0oR where R is an alkyl group of l to 3 carbon atoms and X is H or an alkyl group of l to 2 carbon atoms. .The above acrylic monomers can be used in an amount of about 100 parts by weight with about 2 to 30 parts by weight of another copolymerizable monomer such as styrene, butadiene, ethylene and acrylic acid to provide a suitable polymer for the tooth repairing compositions. Other polymers can be used'such as polyvinyl chloride, cellulose acetate, and a styrene acrylonitrile copolymer providing the resultant composition is radiopaque, has the desired color, index of refraction, strength, wear resistance, thermal expansion and is nontoxic. The filler composition itself generally comprises about 50-90 parts by weight of the glass-ceramic material or other inorganic filler and about 10-50 parts by weight of radiopaque glass. Preferred amounts of the inorganic filler preferably having a low thermal coefficient of expansion are about 60-80 parts by weight INGREDIENTS PERCENT sio, 25-35 A1,o -20 BaO 50-60 An especially useful glass-ceramic for obtaining the best balance of desired properties contains the following ingredients in approximate percent by weight:

INGREDIENTS PERCENT SiO, AI,O, TiO, ZrO, Sb,0, CaO Li,O Na,0 K,O

ing and facing composition as does praseodymium oxide.

The following example illustrates the present invention.

EXAMPLE A series of filler compositions comprising parts by weight ofa barium aluminosilicate glass mixed with 70 parts by weight of a glass-ceramic were prepared and the resultant filler compositions mixed in an amount of about parts by weight with parts by weight of a liquid, solvent-soluble, further curable, methyl methacrylate polymer. The glass-ceramic used was one containing the following ingredients in approximate percent by weight:

INGREDIENTS PERCENT SiO A1 0 TiO ZrO 515,0, CaO Li O Na o K,O

99* was this:

The barium aluminosilicate glass used was one of the following series in which the ingredients are given in weight percent and mole percent.

Weight Percent Mole Percent sio M203 BaO 510 A120 8210 A 40 3o 30 5s 25 17 13 4o 20 40 59 1s 23 c 30 3o 40 4s 2s 25 1) 25 25 5o 42 25 33 E 40 10 50 e1 9 30 F 30 1o 51 10 39 o 20 20 so 36 22 42 x 26 1s 56 44 1s as Y 38.2 15.5 46 59 14 28 INGREDIENTS PERCIIN'I' Si(), 26 Al O, l8 B80 56 Although the preferred radiopaque producing oxide by far is barium oxide, it giving the best color and all around properties to the resultant composition, other radiopaque producing oxides such as strontium can be used. Also suitable but not as good as strontium oxide are lanthanum and other rare earth oxides of the lanthanide series, Nos. 57-71 such as samarium oxide, dysprosium oxide and terbium oxide can be used in which the mass absorption coefficient of the element (including scattering) is generally above about 300 and preferably above about 350 for CuKa, 1.5418 A. The mass absorption coefficient of Ba is given as 359 and lanthanum as 378. However, the lanthanum oxide generally imparts some undesirable color to the tooth fill- The resultant mixture was used as a tooth facing and filling composition, the mixture being formed to the desired shape and the organic binder being cured by heating or at room temperature to thereby remove the solvent and form a thermoset polymer that binds the finely divided filler within its matrix.

The resultant compositions all had an outstanding combination of properties including a color resembling that of natural teeth, strength, wear resistance, abrasion resistance, a low thermal expansion matching that of natural teeth and were radiopaque to X-rays used by dentists. The mass absorption coefficients were calculated for copper Ka radiation which has a wavelength of about 15418 A. From the standpoint of glass processing including a desirable liquidus, compatible index of refraction and absorption coefficient, it is highly preferred that the radiopaque barium aluminosilicate glasses be ones having compositions similar to that of F and G in the above Table. Hence, the optimum glasses contain about 18-32 weight percent SiO 8-22 weight percent A1 0 and about 56-62 weight percent BaO. Glasses in the barium aluminosilicate system shown in the area bounded by line .I of the FIGURE are advantageous because they have low coefficients of thermal expansion in the range of about 55-60 up to 70 or 75 X l0' /C. and have an index of refraction similar to that of natural teeth. The calculated X-ray absorption coefficients of the barium aluminum silicate glasses shown in A through G, X and Y in the Table are as follows:

Mass Absorption Linear Absorption Coefficient Density Coefficient A 83.5 2.7 223 B 101 2.9 293 C 106.9 3.2 342 D 129.8 3.5 454 E 121.5 3.2 388 F 148 3.7 548 G 156.3 4.0 626 X 144.8 3.7 536 Y 1 15.8 3.0 348 "35-44, the liquidus temperatures of the glasses inside the area of line I are within the range of about 1,300C. to 1,700C. and hence are easily melted, processed and formed. The preferred compositions have a liquidus in the range of about l,400 to 1,600 C.

What is claimed is:

l. A composition for use as a filler in tooth filling and facing compositions comprising a finely divided glassceramic material and a barium aluminosilicate glass, said glass-ceramic material having a particle size between 20 and 400 mesh, and said barium aluminosilicate glass consisting essentially of BaO, A1 0 and SiO, in the relative proportions by weight shown inside the area of line I shown in the ternary diagram of the FIGURE and having a coefficient of thermal expansion in the range of about 55 X /C to about 75 X l0 /C, the amount of glass-ceramic material being about 50 to 90 parts by weight and the amount of barium aluminosilicate glass being about 10 to 50 parts by weight, the composition having a color resembling that of natural teeth, having an index of refraction matching that of natural teeth, having desirable hardness, having a relatively low thermal expansion matching that of natural teeth, and being radiopaque.

2. A composition as defined in claim 1 in which the barium aluminosilicate glass consists essentially of BaO, A1 0 and SiO in the relative proportions of.

weight shown inside the area of line II shown in the ternary diagram of the FIGURE.

3. A composition as defined in claim 2 in which 70 parts by weight of a glass-ceramic consisting essentially of SiO-,., Li O, Na 0, K 0, CaO, Sb O A1 0 ZrO and TiO are used with about 30 parts by weight of a glass having the following ingredients in approximate percent by weight:

INGREDIENTS PERCENT sio 25-35 A1201, l0-20 BaO 50-60 4. A composition as defined in claim 3 in which the glass-ceramic contains the following ingredients in approximate percent by weight:

INGREDIENTS PERCENT SiO 67 A1 0 20 TiO 1.7 ZrO; 2

Sb O, .3 C210 3.5 Li,0 4 Na O 0.4 K 0 0.2

and the glass contains the following ingredients in approximate percent by weight:

INGREDIENTS PERCENT so, 26 A110, 18 B210 56 5. A composition as defined in claim 1 in which the particle size of said finely divided glass-ceramic mate- 1 7. A composition as defined in claim l'in which the amount of glass-ceramic material is about 60 to 80 parts by weight and the amount of barium aluminosilicate glass is about 20 to 40 parts by weight.

8. A composition as defined in claim 7 in which the amount of glass-ceramic material is about 70 to parts by weight and the amount of barium aluminosilicate glass is about 25 to 30 parts by weight.

9. A composition as defined in claim 1 in which the barium aluminosilicate glass consists essentially of about 25 to 35 percent by weight SiO about 10 to 20 percent by weight A1 0 and about 50 to 60 percent by weight BaO.

10. A composition as defined in claim 1 in which the barium aluminosilicate glass consists essentially of about 18 to 32 percent by weight Si O about 8 to 22 percent by weight A1 0 and about 56 to 62 percent by weight BaO.

11. A composition as defined in claim 1 in which said barium aluminosilicate glass has an X-ray linear absorption coefficient between 223 and 626. c 

2. A composition as defined in claim 1 in which the barium aluminosilicate glass consists essentially of BaO, Al2O3 and SiO2 in the relative proportions of weight shown inside the area of line II shown in the ternary diagram of the FIGURE.
 3. A composition as defined in claim 2 in which 70 parts by weight of a glass-ceramic consisting essentially of SiO2, Li2O, Na2O, K2O, CaO, Sb3O3, Al2O3, ZrO2, and TiO2 are used with about 30 parts by weight of a glass having the following ingredients in approximate percent by weight:
 4. A composition as defined in claim 3 in which the glass-ceramic contains the following ingredients in approximate percent by weight:
 5. A composition as defined in claim 1 in which the particle size of said finely divided glass-ceramic material is between about 100 and 200 mesh.
 6. A composition as defined in claim 1 in which said glass-ceramic material consists of essentially of SiO2, Li2O, Na2O, K2O, CaO, Sb2O3, Al2O3, ZrO2 and TiO2.
 7. A composition as defined in claim 1 in which the amount of glass-ceramic material is about 60 to 80 parts by weight and the amount of barium aluminosilicate glass is about 20 to 40 parts by weight.
 8. A composition as defined in claim 7 in which the amount of glass-ceramic material is about 70 to 75 parts by weight and the amount of barium aluminosilicate glass is about 25 to 30 parts by weight.
 9. A composition as defined in claim 1 in which the barium aluminosilicate glass consists essentially of about 25 to 35 percent by weight SiO2, about 10 to 20 percent by weight Al2O3 and about 50 to 60 percent by weight BaO.
 10. A composition as defined in claim 1 in which the barium aluminosilicate glass consists essentially of about 18 to 32 percent by weight SiO2, about 8 to 22 percent by weight Al2O3 and about 56 to 62 percent by weight BaO.
 11. A composition as defined in claim 1 in which said barium aluminosilicate glass has an X-ray linear absorption coefficient between 223 and
 626. 